112

Introduction
Ethylene is one of the simplest plant growth
regulators and is known to play a role in many
physiological processes in plants. Seed germination
and growth, abscission, fruit ripening and senes-
cence can all be affected by ethylene (14). It is
believed that the ancient Egyptians and Chinese
were aware of some of these effects and attempted
to artificially control the ripening of figs and pears.
More recently, in the nineteenth century, it was
observed that street lighting (fuelled by town gas
which contained low levels of ethylene) was caus-
ing stunting and other changes to nearby plant
growth (2). Today, although it is well documented
that almost all plants produce ethylene in varying
amounts, understanding how ethylene interacts
with each plant type and the effect this has on
plant development is a very active area of
scientific research.
The ability to control ripening is very important
to the sale of many fresh produce types. Whilst
consumers often want to purchase food that can
be eaten straight away, suppliers may prefer to
market fruit in need of further ripening, to avoid
losses due to over-ripening in transit or storage.
Therefore, the control of the ambient ethylene
concentration is key to prolonging the shelf-life of
many horticultural products.
Various methods of ethylene control are
offered commercially, including several based on
ethylene adsorption/oxidation. However, these
technologies have seen limited uptake, especially in
retail packaging and fresh produce transportation.
In the present paper, we report on the development
of a new palladium (Pd)-based ethylene adsorber,
which works effectively both in synthetic gas
streams and in laboratory-based trials using real
fruit samples. We are now in a position to under-
take real-world testing.
Ethylene Production by Fresh Produce
Fresh fruit and vegetables are generally classi-
fied in one of two ways, depending upon the
mechanism of ripening (5) and their capacity to
produce ethylene (Table I). Climacteric items
release a burst of ethylene during ripening, accom-
Platinum Metals Rev., 2009, 53, (3), 112122
A New Palladium-Based Ethylene
Scavenger to Control Ethylene-Induced
Ripening of Climacteric Fruit
By Andrew W. J. Smith*, Stephen Poulston and Liz Rowsell
Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.; *E-mail: smithawj@matthey.com
Leon A. Terry
Plant Science Laboratory, Cranfield University, Cranfield, Bedfordshire MK43 0AL, U.K.
and James A. Anderson
Surface Chemistry and Catalysis Group, Department of Chemistry, University of Aberdeen, Aberdeen B24 3UE, U.K.
A novel palladium-promoted zeolite material with a significant ethylene adsorption capacity
at room temperature is described. It was characterised by diffuse reflectance infrared Fourier
transform spectroscopy (DRIFTS) and transmission electron microscopy (TEM) to show
palladium particles dispersed over the support. Initial measurements of the ethylene adsorption
capacity were conducted with a synthetic gas stream at a higher ethylene concentration
than would normally be encountered in fruit/vegetable storage, in order to obtain an accelerated
testing protocol. Further laboratory-based trials on fruit samples show that the palladium-
promoted zeolite material can be effective as an ethylene scavenger to prolong the shelf-life
of fresh fruits.
DOI: 10.1595/147106709X462742
panied by an increase in respiration, whereas non-
climacteric produce do not vary their rate of
ethylene production in this fashion. Exogenous
ethylene (typically < 0.11.0 l l
1
) can initiate
ripening in many climacteric fruit which then can
lead to autocatalytic production of ethylene by the
fruit. Climacteric fruits, which include bananas,
avocados, nectarines and pears, ripen after harvest,
typically by softening, changing colour and becom-
ing sweeter (6). The latter class, including
strawberries, grapes and pineapples do not ripen as
dramatically after harvest, but rather senesce, lead-
ing to discolouration, unpleasant odour, shrinkage
and general rotting. In such cases, the challenge to
maintain product quality is paramount. Other fresh
produce types are sensitive to ethylene even
though their ethylene production is very low for
example, potato tubers, bulb onions, broccoli and
spring cabbage, along with some cut flowers.
To artificially reproduce the natural ripening
process, ethylene can be introduced during storage.
This process is used in the fruit industry on fresh
produce such as bananas, avocadoes and mangoes
(7). As well as such deliberate exogenous introduc-
tion, the level of ethylene can rise due to ethylene
emission from stored fresh produce or from acci-
dental sources such as forklift truck exhaust
emissions. For this reason, the industry prefers to
use electric vehicles in fresh food storage areas to
minimise the risk of the fresh produce coming into
contact with ethylene gas.
Excessive or uncontrolled levels of ethylene can
result in a number of problems. For example, the
premature ripening of fruits and vegetables, the
fading and wilting of cut flowers and the loss of
green colour and increase in bitterness of vegeta-
bles are common problems when ethylene levels
have not been properly managed.
Ethylene-Sensitive Plants
Plants, flowers and buds are also sensitive to
ethylene (see Table II for examples) and some
release ethylene gas when they are cut or damaged.
Some of the most detrimental effects of ethylene
on plants are:
Partial or incomplete flower abortion;
Retarded plant growth;
Growth abnormalities such as excessive leafi-
ness or the stimulated growth of daughter
bulbs;
Shortened vase lifespan of cut flowers (abscis-
sion of leaves and flower petals);
Inhibited development of immature (unopened)
flower buds;
Accelerated senescence of all types of plants;
Susceptibility to disease.
Ethylene Removal Technologies
In many instances, ethylene concentrations can
be controlled by ventilation of the area containing
Platinum Metals Rev., 2009, 53, (3) 113
Table I
Ethylene Production from Different Fresh Produce Types
Low Moderate High Very high
(< 1.0 ml kg
1
h
1
) (110 ml kg
1
h
1
) (10100 ml kg
1
h
1
) (> 100 ml kg
1
h
1
)
Pineapple, artichoke, Banana, mango, Apricot, nectarine, Apple, avocado,
cauliflower, broccoli, plum, tomato pear, peach cherimoya,
date, orange, rhubarb, passion fruit
spinach, beetroot,
green asparagus,
celery, lemon, onion
Table II
Different Degrees of Ethylene Sensitivity amongst
Cut Flower Species
Low Moderate High
Sensitivity Sensitivity Sensitivity
Tulip, Lily, freesia, Carnation,
daffodil agapanthus, Geraldton
alstroemeria, waxflower
anemone,
dahlia
the fresh produce. This can be aided by container
designs that allow for air circulation. However,
ventilation is not always appropriate; for example,
it cannot be used in sealed environments, such as
controlled atmosphere storage or retail packaging.
There are a number of ethylene removal technolo-
gies available:
Catalysts. Often based on platinum/alumina,
these operate at elevated temperature
(> 200C) and catalytically oxidise ethylene to
carbon dioxide (CO
2
) and water (8). There are
also reports of the use of photocatalytic oxida-
tion of ethylene using titanium dioxide (TiO
2
),
which can occur at room temperature (9).
Stoichiometric oxidising agents. Mostly based on
potassium permanganate (KMnO
4
), which
again oxidises ethylene and is itself reduced.
Though some CO
2
and water is produced,
some partially oxidised species such as car-
boxylic acids may also be formed.
Sorbents. These materials work by sorption of
the ethylene and are often based on high sur-
face area materials, including activated carbon,
clays and zeolites.
Ethylene Blocking Technologies
A different approach is to inhibit ethylene
action in the produce itself, which can in turn
reduce the amount of ethylene released by the pro-
duce into the container or storage area. Several
chemicals have been shown to act as ethylene
inhibitors, including both volatile and aqueous
treatments:
1-Methylcyclopropene (1-MCP). 1-MCP is the most
widely used commercial volatile ethylene
inhibitor, which blocks ethylene binding sites.
It is applied exogenously as a gas and has been
widely applied to fruit (particularly apples) and
flowers. 1-MCP is sold commercially as
SmartFresh
SM
(10) into the fresh produce
industry and as EthylBlock
TM
into the floral
industry.
Silver thiosulfate (STS). The use of this material is
largely restricted to cut flowers and it is sold
commercially under the trade name Chrysal
AVB

. It is applied by putting the cut flower

stems in a solution containing the STS.
Aminoethoxyvinylglycine (AVG). This material is
sold commercially as ReTain

and acts as a
plant growth regulator by blocking the produc-
tion of ethylene in the plant tissue. It is sprayed
onto the fruit, usually 1 to 3 weeks prior to
harvesting.
New Palladium-Based Ethylene
Scavenging Technology
In this paper, we report on the discovery by
Johnson Matthey scientists of a novel palladium-
promoted material with a significant ethylene
adsorption capacity at room temperature (11). A
wide range of materials were synthesised and
screened for activity. Pd gave by far the best per-
formance of the promoter metals tested. The
material is a palladium-impregnated zeolite giving
finely dispersed palladium particles.
Initial testing was conducted with a synthetic
gas stream at a higher ethylene concentration than
would normally be encountered in fruit/vegetable
storage, in order to obtain an accelerated testing
protocol for measuring ethylene adsorption
capacity. Ethylene adsorption capacity measure-
ments were carried out at room temperature
(21C) in a plug flow reactor using 0.1 g of active
Pd-based material with a gas composition of 200
l l
1
ethylene, 10% (v/v) oxygen balanced with
helium, at a flow rate of 50 ml min
1
, with and
without ca. 100% relative humidity (RH). Reactor
outlet gas concentrations were analysed using a
Thermo Onix ProLab mass spectrometer
(Thermo Onix, Houston, Texas, U.S.A.). A
mass:charge ratio of either 26 or 27 was used for
ethylene, as the use of nitrogen as a diluent gas
leads to the presence of a large peak at m/z = 28.
A value of m/z = 44 was used for CO
2
. Ethylene
uptake capacity was measured using a simple
breakthrough measurement, in which the total
integrated ethylene removal was determined after
the outlet ethylene concentration from the reactor
had reached the inlet ethylene concentration,
showing that the adsorber was saturated with
ethylene (12).
The Pd-based material typically removed all
measurable ethylene until breakthrough occurred.
A typical example of an ethylene breakthrough
Platinum Metals Rev., 2009, 53, (3) 114
measurement under humid conditions is shown in
Figure 1. Under these conditions the Pd-promoted
material was found to have an ethylene adsorption
of 4162 l g
1
under ca. 100 % RH. This perfor-
mance was increased to 45,600 l g
1
under dry
conditions.
Further experiments were carried out at room
temperature in a sealed, unstirred batch reactor
(0.86 l) with 0.1 g active Pd-based material and an
initial gas composition of 550 l l
1
ethylene, 40%
(v/v) air balanced with argon. Selected gas concen-
trations were measured at hourly intervals with a
Varian CP-4900 Micro-GC (Varian, Inc, Palo Alto,
California, U.S.A.). Gas samples (40 ms duration)
were taken via an automated recirculating sampling
system. Column and injector temperatures were set
at 60C and 70C, respectively. The 0.15 mm
diameter, 10 m long column was packed with
PoraPLOT (porous layer open tubular) Q station-
ary phase. Ethylene and CO
2
were calibrated
against 10 l l
1
ethylene balanced with air and 5%
(v/v) CO
2
balanced with Ar (Air Products Europe,
Surrey, U.K.). A thermal conductivity detector was
used with He carrier gas at 276 kPa inlet pressure.
Peak integration was carried out within the Varian
STAR software.
Under these conditions, CO
2
and ethane pro-
duction were observed, as plotted in Figure 2.
The ethane is likely to be produced by the hydro-
genation of adsorbed ethylene, the hydrogen being
generated by the partial dissociation of ethylene.
The selectivity to ethane varies with experimental
conditions but is typically no more than the maxi-
mum value of ~ 10% observed under the
conditions tested here. Ethane can be produced by
plants in response to stress (13) and has not previ-
ously been reported to be detrimental to plants in
the concentration range reported here. It is clear,
however, that the palladium-based material is act-
ing largely as an adsorber rather than as a catalyst.
The mechanism of reaction is discussed further in
this article by interpretation of diffuse reflectance
infrared Fourier transform spectroscopy (DRIFTS)
data.
Characterisation of the palladium-based mater-
ial was carried out to determine the Pd
distribution through the support. Transmission
electron microscopy (TEM) analysis (Figure 3)
showed that the palladium particles (bright parti-
cles) are dispersed over the support material. The
average size of the palladium particles in Figure 3
was calculated to be 1.7 nm. Scanning electron
microscopy (SEM) analysis (not shown) also iden-
tified some larger palladium particles with
diameters around 20 to 40 nm. These results cor-
respond well with CO chemisorption data which
gave a metal dispersion of ~ 15 %. From this dis-
persion value, a slightly larger average size of the
palladium particles would be expected. This is
consistent with the observation of many small and
some larger particles by TEM (Figures 3 and 4)
and SEM.
Platinum Metals Rev., 2009, 53, (3) 115
200
150
100
50
0 500 1000 1500 2000 2500 3000 3500
E
t
h
y
l
e
n
e

c
o
n
c
e
n
t
r
a
t
i
o
n
,

l

l

1
Time, s
Fig. 1 Ethylene
breakthrough graph of the
Pd-based material in humid
gas conditions. Ethylene was
monitored using the mass 26
signal on a mass
spectrometer (mass 26 and
27 gave very similar
breakthrough profiles)
EthyleneMetal Interaction via
DRIFTS Analysis
In order to gain further information regarding
the processes involved in ethylene removal, a
vibrational spectroscopic study was performed
to probe the interactions between the ethylene
and the Pd-promoted scavenger. DRIFTS was
used to characterise the species adsorbed on the
ethylene scavenger after exposure to ethylene, in
the presence and absence of oxygen and water
vapour.
DRIFTS allows spectra to be obtained of pow-
dered samples in the presence of gaseous
atmospheres. It produces infrared spectra of the
diffusely scattered radiation in the reflectance
mode (Figure 5), which are analogous to those col-
lected in the more conventional transmittance
mode. Disadvantages of this method include the
appearance of artefacts resulting from the collec-
tion of specularly reflected radiation. It is also
difficult to perform quantitative studies, since both
scattering and absorption coefficients must be
considered. By contrast, only the latter is required
to quantify adsorbed species when spectra are col-
lected in the transmittance mode and converted to
absorbance (14). The key advantages of this
method are that no sample preparation is neces-
sary and that the cells can be operated in plug flow
mode with the reactant gases being forced to trav-
el through the bed of powdered scavenger
material.
Commercial DRIFTS cells are readily available
which allow the collection of spectra of powdered
samples at ambient or elevated temperatures,
while controlling the composition of the gaseous
atmosphere. In the study performed here, the out-
let port of the DRIFTS cell was coupled to a
quadropole mass spectrometer (QMS) via a heated,
glass-lined capillary. This permitted continual
monitoring of ethane (m/z = 30), carbon dioxide
(m/z = 44) and ethylene (a value of m/z = 27 was
selected for this experiment) during exposure to
ethylene and during subsequent temperature-pro-
grammed desorption (TPD) measurements.
Experiments were performed by exposing samples
Platinum Metals Rev., 2009, 53, (3) 116
Time, h
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

C
O
2
a
n
d

e
t
h
y
l
e
n
e
,

l

l

1
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

e
t
h
a
n
e
,

l

l

1
4 8 12 0
0
100
200
300
400
500
100
80
60
40
20
0
Ethylene (Pd scavenger)
Carbon dioxide
Ethane
Fig. 2 Gas
concentrations
in a batch
reactor initially
containing
550 l l
1
ethylene*,
along with 0.1
g of the
Pd-promoted
ethylene
scavenger
*Note: Some
ethylene has
been removed
by the
scavenger
prior to the
first injection
10 nm
Fig. 3 TEM image of the Pd-promoted zeolite material
showing nanometre size palladium particles (bright
areas) on the zeolite support
with and without Pd, at ambient temperature, to a
flow of ethylene in nitrogen with the addition of
either no other gases, air or air and water. After a
period of exposure to these gaseous atmospheres,
the ethylene stream was switched off and a TPD
measurement was performed in the presence of
the remaining gases. Spectra were also obtained of
samples that had been exposed to ripened fruit.
The Fourier transform infrared (FTIR) spec-
trum of ethylene in nitrogen flowing through the
cell, in the absence of scavenger, gave main fea-
tures at 3112 cm
1
(
9
, CH asym.), 2992 cm
1
(
11
, CH sym.), 2048 cm
1
(2
10
, CH
2
rock-
ing), 1889 cm
1
(2
7
, CH
2
out-of-plane) and
1446 cm
1
(
12
, CH
2
in-plane). The absence of
bands for the IR inactive (totally symmetrical)
modes at 1623 cm
1
(
2
, C=C) and 1343 cm
1
(
3
, CH
2
in-plane) should be noted, although it is
expected that any interaction with the adsorbent
might permit these modes to be detected as the
symmetry is lifted. These interactions might also
be expected to shift the frequencies away from the
gas phase values listed above.
FTIR spectra of a sample exposed to fruit
(Figure 6(a)) showed features at 1467, 1460, 1434
and 1382 cm
1
. FTIR spectra of the Pd-free zeolite
showed only very weak features, including a band
at 1439 cm
1
which could be assigned to the pres-
ence of adsorbates resulting from exposure to
ethylene (Figure 6(c)). However, these features
were absent following heating to 50C in air. The
narrow shape of the feature at 1439 cm
1
, and the
appearance of a single rather than a double compo-
nent (as in the gas phase), confirms that this
feature can be assigned to an adsorbed state,
although the limited shift ( = 7 cm
1
) with
respect to the gas phase feature (due to the
12
,
CH
2
in-plane) would suggest a very weakly bound
state. This was confirmed by the disappearance of
bands at this frequency when the sample was heat-
ed in air to 50C. Note that this ease of removal
was not the case for the sample containing Pd
(Figure 6(b)). This, along with the detection of
other infrared bands (at 1467 and 1382 cm
1
) when
Pd was present, would indicate that the metal
played a significant role in the retention of the
adsorbate and in the dominant adsorbed state. The
relative intensities of the features indicate that the
Platinum Metals Rev., 2009, 53, (3) 117
N
u
m
b
e
r

o
f

P
d

p
a
r
t
i
c
l
e
s
Pd particle size, nm
0.5 1 1.5 2 3.5 2.5 3 4 4.5 5 >5
0
40
60
80
20
100
120
140
Fig. 4 Particle size distribution of
palladium in the palladium-promoted
zeolite material, as determined from the
TEM image in Figure 3
Incident beam
Diffuse reflectance
Sample
Fig. 5 Scheme showing the scattering of light from a
powdered sample and the collection of the diffusely
scattered component for DRIFTS analysis
presence of Pd was essential in order to achieve
the 45,600 l g
1
adsorption capacity obtained
under dry conditions. The similarities between the
features resulting from exposing the sample to
fruit (Figure 6(a)) and to exogenous ethylene, in
particular the features at 1467 and 1382 cm
1
, are
strong evidence that similar adsorbed species exist
in both cases. Under these conditions, the CH
stretching region gave two dominant bands at
2969 and 2865 cm
1
, which are consistent with
expectations for CH
3
species (Figure 7).
The transformation from C
2
H
4
to adsorbed
species containing CH
3
would be consistent with
the development of ethylidyne (CCH
3
) species (15,
16). In these species, the carbon forms three bonds
to the surface metal atoms (Figure 8(c)), probably
on three-fold hollow sites of Pd(111) type facets
(17). Such an assignment would be consistent with
the detection of the 1467 and 1382 cm
1
band pair
(Figure 6) arising from the corresponding CH
3
deformation modes. The formation of a hydrogen
atom for each ethylidyne species generated would
Platinum Metals Rev., 2009, 53, (3) 118

180 0 1 600 1400 1200
R
e
f
l
e
c
t
a
n
c
e
/
%
Wavenumber/cm
-1
20%
(a)
(b)
(b)
(a)
(c)
(c)
Wavenumber, cm
1
R
e
f
l
e
c
t
a
n
c
e
,

%
20 %
1800 1600 1400 1200
(a)
(b)
(c)
(a)
(b)
(c)
Fig. 6 DRIFT spectra of:
(a) the Pd-promoted zeolite
material following exposure to
fruit,
(b) the Pd-promoted zeolite
material exposed to a flow of
ethylene/nitrogen at 25C,
(c) Pd-free zeolite exposed to
ethylene in nitrogen at 25C

3200 3 150 310 0 3050 30 00 2950 2900 28 50 2800 2 750 2700
R
e
f
l
e
c
t
a
n
c
e
/
%
Wavenumber/cm
-1
(a)
(b)
(c)
10%
Wavenumber, cm
1
R
e
f
l
e
c
t
a
n
c
e
,

%
10 %
(a)
(b)
(c)
3200 3150 3100 3050 3000 2950 2900 2850 2800 2750 2700
Fig. 7 DRIFT spectra of the
Pd-promoted ethylene scavenger:
(a) before exposure to ethylene,
(b) after exposure to a flow of
ethylene in nitrogen at 25C,
(c) after exposure to a flow of
ethylene in air at 25C
explain the formation of ethane following initial
exposure of the scavenger to ethylene (Figure 2),
which was observed in the mass spectrometry (MS)
trace (m/z = 30) recorded during the FTIR mea-
surements. The surface selection rule states that
vibrations parallel to a metal surface should not be
detected, due to the creation of an opposing image
dipole on the metal. This means that the CH
3
asymmetric and CH
3
asymmetric modes at 2969
and 1467 cm
1
should be absent from the spec-
trum. However, this rule will be relaxed for very
small metal crystallites of the order of 2 nm and
below and where extended flat facets are absent
due to the presence of steps and edges.
Such a description of the morphology is consis-
tent with the TEM image presented (Figures 3 and
4). This assignment cannot be confirmed from the
expected absorption at around 1130 cm
1
(CC),
due to absorption by the support in this region.
Bands due to ethylidyne were diminished in spec-
tra recorded after heating the sample in nitrogen to
150C. If air was present during this thermal treat-
ment, then CO
2
was detected by MS as a complete
oxidation product. Below this temperature, FTIR
evidence for partial oxidation included the detec-
tion of carboxylate type species and a band at 2125
cm
1
due to CO adsorbed at surface oxidised Pd
sites. The latter was detected in spectra of the sam-
ple recorded at 100C, indicating that the onset of
oxidation took place well below the temperature of
complete oxidation.
An MS trace was recorded during the collection
of spectra with exposure to ethylene. This showed
a breakthrough shape which was strongly depen-
dent on the composition of the gas phase, with the
greatest removal of ethylene occurring during treat-
ment in nitrogen. The presence of air or air and
water reduced the adsorption capacity.
Additionally, the presence of air or air and water
modified the predominant modes of adsorption,
with four bands now appearing in the CH stretch-
ing region. In addition to the pair at 2957 and 2865
cm
1
which have already been assigned to the CH
3
modes of ethylidyne in the absence of air or water,
a further pair at 2934 and 2853 cm
1
were detected,
although these were very weak when water was
present. These features are consistent with expec-
tations for CH
2
groups, although the vibrational
frequencies are relatively low for vinyl species. Di-
species of adsorbed ethylene (Figure 8(b)) give
lower frequency CH modes than -C
2
H
4
(18)
(Figure 8(a)), although the former are less favoured
in the presence of adsorbed oxygen (18). The pres-
ence of oxygen in the system also led to the
appearance of a species giving a maximum at 1514
cm
1
, which was absent for the air-free system.
A similar feature was found at 1510 cm
1
in
electron energy loss spectroscopy (EELS) spectra
of ethylene on oxygen covered Pd(100). This was
assigned to CH
2
, so it would be tempting to
assign the surface species to vinyl intermediates
such as HCCH
2
(17). However, an alternative
assignment, consistent with the known stepwise
dehydrogenation of ethylene (19), is that the addi-
tional maxima at 2934 and 2853 cm
1
represent
vibrations due to the CH
3
groups of ethylidene
(CHCH
3
), where the expected full conversion to
ethylidyne, observed in the absence of air and
water (18), is hindered due to the presence of the
co-adsorbates which limit the activation and
dissociation of the CH bond. The lesser extent of
CH dissociation at room temperature, and subse-
quently the lesser population of the surface by
adsorbed hydrogen, would explain the reduced
Platinum Metals Rev., 2009, 53, (3) 119
(a) (e) (b) (c) (d) (f)
Pd Pd Pd Pd Pd Pd
Fig. 8 Potential adsorbed species following exposure of the Pd-containing scavenger to ethylene:
(a) -bonded, (b) di- bonded, (c) ethylidyne, (d) ethylidene, (e) vinylidene and (f) vinyl
ability of the surface to liberate ethane resulting
from ethylene hydrogenation during the initial
exposure stages.
In summary, the surface speciation is some-
what dependent on the gas mix and the moisture
content. However, the DRIFTS study has identi-
fied the key role of the palladiumethylene
interaction and the benefit that this has on binding
ethylene to the zeolite surface.
Fresh Produce Research
The use of platinum group metals including pal-
ladium in different forms and on different supports
for ethylene removal from fruit and vegetables has
been investigated by other authors in the past (20,
21). Bailn et al. at University Miguel Hernndez
have recently published results on delaying tomato
decay using a combination of controlled atmos-
phere packaging and a granular-activated carbon
(GAC) or GAC impregnated with a palladium-
based catalyst (22). Martnez-Romero et al. at the
same University have also reported the use of a car-
tridge heater device (optimally running at 175C)
joined to activated carbon containing palladium for
ethylene removal above room temperature (23).
In contrast, the new material described here
consists of a specific combination of a precious
metal with a zeolite and removes significant
amounts of ethylene at low temperature (5C) and
room temperature. In order to test the material
under realistic conditions, the active material has
been evaluated in collaboration with the Plant
Science Laboratory at Cranfield University, U.K.
Bananas were included in the initial studies, as the
role of ethylene in initiating ripening in these fruits
is well documented (24, 25). Initial findings, now
published (2), have demonstrated for the first time
that the presence of a palladium-based scavenger
was effective at removing ethylene to below phys-
iologically active levels for preclimacteric green
bananas and green avocado fruits.
Reduced CO
2
production and control of the
colour change from green to yellow was observed
for the preclimacteric bananas (Figure 9). The
palladium-promoted ethylene scavenger was also
found to be far superior to a KMnO
4
-based ethyl-
ene adsorber when used in low amounts at high
relative humidity. No adverse effects on fruit qual-
ity or subsequent ripening were observed after
removal of the ethylene scavenger material.
Similar experiments were also conducted on
avocados. Results showed that exogenous and
endogenous ethylene concentration was reduced
significantly with increasing amounts of the Pd-
promoted material. In the presence of
Pd-promoted material, ethylene was removed to
below physiologically active levels. The effect of
ethylene on the colour of avocado cv. Hass fruits
in the presence or absence of the palladium mate-
rial is shown in Figure 10. Fruit held in the
presence of 100 mg or 1000 mg of the Pd-promot-
ed material for three days were generally greener,
and thus less ripe, than control fruit after seven to
ten days (Figure 10).
Furthermore, when avocados were treated with
ethylene and then subsequently held in the pres-
ence of the Pd-promoted material (1000 mg) after
day 1, ethylene was removed to below physiologi-
cally active levels. Despite the climacteric phase
having been initiated for these fruits, the
Platinum Metals Rev., 2009, 53, (3) 120
Fig. 9 Colour of a five-day-old banana cv. Cavendish fruit previously held for three days at 16C in 3 l sealed jars
containing the Pd-promoted ethylene scavenger material (050 mg) and previously treated with (+E) or without (E)
100 l l
1
ethylene when at the preclimacteric stage (i.e. green) at day 0
E
+E
0 mg 50 mg 40 mg 30 mg 20 mg 10 mg
subsequent total removal of ethylene resulted in
better maintenance of fruit firmness as compared
to controls. This suggests that the normal and
expected climacteric respiratory rise has been dis-
rupted. Therefore, for the first time an ethylene
scavenger has been shown to be capable of extend-
ing shelf-life even when the climacteric respiratory
rise has already been initiated.
Current work is focused on comparing the effi-
cacy of the Pd-promoted ethylene scavenger to
1-MCP for the control of ripening in avocado fruit,
and the resultant effect on non-structural carbohy-
drates and fatty acid methyl esters.
Conclusions
The results from this study demonstrate that
the Pd-promoted ethylene scavenger described
here is effective for the control of ethylene to pro-
long the shelf-life of climacteric fresh produce
such as bananas and avocados. The material has
the potential to be used commercially, as an alter-
native and/or supplemental treatment to 1-MCP.
The technology does not require elevated temper-
ature to remove ethylene, and the choice of zeolite
support material makes it suitable for most fresh
produce and floral applications under conditions
of high humidity and low or room temperature.
Future research will elucidate further uses of the
Pd-promoted ethylene scavenger.
Acknowledgements
The authors would like to thank Anglo
Platinum for sponsoring the research and develop-
ment in this area.
Platinum Metals Rev., 2009, 53, (3) 121
+E
E
0 mg 100 mg 1000 mg* 1000 mg
Fig. 10 Colour of a seven-day-old
avocado cv. Hass fruit previously
held for three days at 12C in 3 l
sealed jars containing the
Pd-promoted ethylene scavenger
material (0, 100 or 1000 mg) and
previously treated with (+E) or
without (E) 100 l l
1
ethylene
when at the preclimacteric stage
(i.e. green) at day 0
* The Pd-promoted material
(1000 mg) was put into the jars
after day 1, following treatment of
the fruit with or without 100 l l
1
ethylene
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The Authors
Dr Stephen Poulston is a Principal
Scientist at JMTC. His main interests lie
in heterogeneous catalysts and
sorbents.
Dr Elizabeth Rowsell is a Research
Manager at JMTC. She is responsible
for managing the Ethylene Scavenger
research project and developing new
applications for platinum group metals.
Dr Andrew W. J. Smith is a Principal
Scientist at the Johnson Matthey
Technology Centre (JMTC), Sonning
Common, U.K. He is a synthetic
inorganic chemist with experience in
materials, glass technology and catalyst
preparation. He is interested in
developing new materials and their
applications in heterogeneous catalysis.
Dr Leon Terry is a Senior Lecturer in
Plant Science and Head of the Plant
Science Laboratory at Cranfield
University, U.K. The Plant Science
Laboratory is one of the largest
university-based groups in the EU
dedicated to research, consultancy and
education in post-harvest technology of
fresh produce.
Professor Jim Anderson is Head of Chemistry (Research) at the
University of Aberdeen, U.K. His main interests lie in the areas of
supported metal catalysis and mixed oxide-based acid catalysis and
in the use of infrared spectroscopy for site quantification and
interpretation of selectivity effects in catalysis.